The one-on-one time at Criniti's restaurant in Castle Hill was organised as part of a new leadership program launched by Castle Hill MP Dominic Perrottet in November.

"The key message I took from the commissioner's [15-minute] address to the students was if you lose your integrity you have nothing left," said Mr Perrottet, the only other non-student to attend the dinner.

Students asked questions after Commissioner Scipione's presentation which included reflections on his experiences as commissioner and as a husband and father.

With the NSW Police since 1980, Commissioner Scipione is a recipient of the Australian Police Medal and the National Medal.

"I'm sure every one of the participating students walked away with a renewed vision of leadership, as well as some practical suggestions on being the best possible representatives of ourselves, our schools and our country," said Samantha Marshall, of Gilroy Catholic College, who presented the commissioner with a gift on behalf of the students.

The 16 year 12 students chosen for the program will walk the arduous 90-kilometre Kokoda Track in Papua New Guinea during Schoolies Week.

They will also meet eight of Australia's finest leaders at mentoring dinners like this one. They include Westpac chief executive Gail Kelly, NSW Supreme Court Chief Justice Tom Bathurst and former Prime Minister John Howard.

The next will be hosted by businessman David Kirk, a former World Cup-winning rugby captain.